The Electronic Spectra

of Complexes
The spectrum of d3 [Cr(NH3)3]+3
 Spectroscopic Term Symbols
microstates => number of different ways e-
can be placed in a given set of orbital sites
 Spectroscopic Term Symbols
n!
# microstates = --------
e! h!
where n => max # e-s in sublevel
(sum of e + h)
e => #e- in case study
h => #"holes" in case study
(hole is a site not occupied by an e-)
Example: p2 case
2 electrons in a p orbital
n!
# microstates = --------
e! h!

6! 5*6
= ------ = ---------
2!*4! 1*2
= 15 (4! factors out)
Example: p2 case
2 electrons in a p orbital
L
+1
0
-1
S

s = +1/2 s = -1/2
Example: p2 case
2 electrons in a p orbital
term symbols => 2S + 1L
ground state => highest S
highest L
 1D Term Microstates
1D L
+2 +1 0 -1 -2

S 0 0 0 0 0
1S Term Microstate
1S L
0

S 0
 3P Term Microstates
3P L
+1 0 -1
+1
S 0
-1

thus, ground state is the 3P term

Example: p2 case
2 electrons in a p orbital
the various terms for p and d electron
combinations
J=|L + S|
therefore, 3P term has
J = 2, 1, or 0 3P 3P 3P
2 1 0
 J Values
number of J values:
S < L 2S + 1 values of J
L<S 2L + 1 values of J
Hund's Third Law
• ground state lowest J for less than 1/2 filled
shell
• highest J for more than 1/2 filled shell
 Atomic Term Symbols
L= 0 1 2 3 4 5 6
S P D F G H I
 Selection Rules
allowed
• ground and excited states for a possible
transition possess the required
characteristics
forbidden
• ground and excited states for a possible
transition do not possess the required
characteristics
 Selection Rules
• selection rules are based on idealized
theoretical models
• some “forbidden transitions” appear in real
spectra because the “real molecule” does
not fit the idealized theoretical model
 LaPorte’s Rule
• in centro-symmetric environments,
transitions can only occur between states of
opposite parity ( u -> g; g -> u)
– allowed
• d --> p; s --> p
• intense lines;   
– forbidden
• d --> d; s -->d
• weak line;  
 Other Observed Transitions
• Non-bonding to antibonding
– in octahedral symmetry
– t2 e*
• weak line;  
– in tetrahedral symmetry
–e t2*
• weak line;  
 d 2 Case
L
+2
+1
m 0
-1
-2
S

+1/2 -1/2
 Term
S = +1/2 S = -1/2
L=2
L=1
L=0
L = -1
L= -2
Correlation Diagram for d1
 d2 Case
10! 9*10
#microstates = ---------- = ---------- = 45
2!*8! 2
 d2 Configuration
Term Number of States
1G 9x1 = 9
3F 7x3 = 21
1D 5x1 = 5
3P 3x3 = 9
1S 1x1 = 1
Total = 45
d2 Configuration
Tanabe-Sugano
diagram for d2
configuration
Noncrossing Rule
Tanabe-Sugano
diagram for d2
configuration
d3 [Cr(NH3)3]+3 spectrum

28,500 cm-1 21,550 cm-1 28,500

= 1.32
21,550
d2, d3, d7, and d8 Octahedral and
Tetrahedral with Bending
 Tanabe-Sugano
diagram for d2
configuration
4A
2  4T => 21,550 cm-1
2

o/B = 21,550/B = 32.8

B = 657 cm-1

32.8
 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case
absorption bands:
– 7.15 kK 1 = 4T1g -> 4T2g

– 15.2 2 = 4T1g -> 4T2g

– 19.2 3 = 4T1g(F) -> 4T1g(P)

 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
– 7.15 kK 1 = 4T1g -> 4T2g
– 15.2 2 = 4T1g -> 4T2g
– 19.2 3 = 4T1g(F) -> 4T1g(P)

1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 7.15 kK 2 = 15.2 3 = 19.2
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
2 - 1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 7.15 kK 2 = 15.2 3 = 19.2
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
2 - 1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
Dq = 0.80 kK
 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from 1
c = 1 - 8Dq
= (7.15 - 8(0.80))kK = 0.8 kK
 EXAMPLE:Calculate Dq
and B for [CoF6]-4.
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from 2
c = 2 - 18Dq
= (15.2 - 18(0.80))kK = 0.8 kK
 EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK; c = 0.80 kK
15B = 3 - 6Dq - 2c
B = (3 - 6 Dq - 2c)/15
= (19.2 kK - 6(0.80kK) - 2(0.80kK))/15 = 0.85 kK
Spectra of [Co(en)3]-3 and [Co(ox)3]-3

Complex   
A A A
[Co(ox)3]-3 6061 4202 13699
[Co(en)3]-3 4673 3390 12346
Spectra of [Co(en)3]-3 and [Co(ox)3]-3

Complex   
A A A
[Co(ox)3]-3 6061 4202 13699
[Co(en)3]-3 4673 3390 12346
 A Summary
of the Charge
Transfer
Transitions
in an
Octahedral
Complex
Absorption Spectrum of [CrCl(NH3)5]+2

d3 case